Light-sensitive polymers

ABSTRACT

A NOVEL CLASS OF LIGHT-SENSITIVE POLYMERS AND THEIR USE IN PHOTOGRAPHIC REPRODUCTION IS DESCRIBED WHICH CONTAINS A 1-ARYLMETHYLENEINDENE GROUP OR A 5-ARYLMETHYLENE-2 (5&#39;&#39;)-FLURANONE GROUP ATTACHED OT A POLYMER BACKBONE.

United States Patent 3,694,411 LIGHT-SENSITIV E POLYMERS John A. Ford,Jr., Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y.N0 Drawing. Filed Aug. 1, 1969, Ser. No. 846,958 Int. Cl. C08g 43/00;C08f 27/00 US. Cl. 260-47 EP 10 Claims ABSTRACT OF THE DISCLOSURE Anovel class of light-sensitive polymers and their use in photographicreproduction is described which contains a l-arylmethyleneindene groupor a -arylmethylene-2 (5H)-furanone group attached to a polymerbackbone.

This invention relates to photographic reproduction. In a particularaspect it relates to a novel class of lightsensitive polymers and theuse of such polymers in the preparation of photographic images.

It is known in the photographic art to reproduce images by processeswhich involve imagewise exposure of a coating of a radiation-sensitivematerial, the solubility of which is differentially modified by theaction of radiation, and subsequent treatment of the coating with asolvent or solvent system which preferentially removes portions of thecoating in accordance with its exposure to light. Such processes havebeen employed to prepare lithographic printing plates, stencils,photoresists, and similar photo mechanical images. Among theradiation-sensitive materials which have been used in such processes,are lightsensitive polymers which are insolubilized or hardened onexposure to light. Typical of these radiation-sensitive materials arethe cinnamic acid esters of polyvinyl alcohol such as are described inMinsk US. Pat. 2,725,372.

The dilferent applications in which light-sensitive polymers are usedrequires that such polymers be available with a variety of photographicand physical characteristics. Thus, there is a continual search fornovel lightsensitive polymers which improve upon and differ fromexisting light-sensitive polymers. I have found a novel class oflight-sensitive polymers which have high photographic speed and a widerange of spectral response even in the absence of a sensitizer.Unsensitized light-sensitive polymer layers are often desired forcertain photomechanical applications since fluorescence of thesensitizer often results in poor resolution in the photomechanicalimage.

Accordingly, it is an object of this invention to provide a novel classof light-sensitive polymers.

It is a further object of this invention to provide a novel class oflight-sensitive polymers having high photographic speed and a wide rangeof spectral response.

It is a further object of this invention to provide novellight-sensitive polymers which have high photographic speed and whichare sensitive to radiation in the visible region of the spectrum in theabsence of a sensitizer.

It is another object of this invention to provide photosensitivecompositions and elements containing this novel class of light-sensitivepolymers.

It is still another object of this invention to provide processes forpreparing photomechanical images employing these novel light-sensitivepolymers.

The above and other objects of the invention will be- "ice come apparentto those skilled in the art from the further description of theinvention which follows.

In accordance with the present invention there is provided a novel classof light-sensitive polymers which con tain as the light-sensitive moietya l-arylmethyleneindene group or a S-arylmethylene-Z(5H)-furanone groupattached to the polymer backbone. The point of attachment of thelight-sensitive moiety to the polymer backbone can either be on theindene or furanone nucleus or on the aryl group. When the polymerbackbone is derived from a hydroxyl-containing polymer, thelight-sensitive moiety is attached through a carbonyloxy linkage; whenthe polymer backbone is derived from a polymer containing reactive aminogroups, the attachment is through an amido linkage; and when the polymerbackbone is derived from a polymer containing reactive anhydride groups,the attachment is through an oxycarbonyl linkage.

The light-sensitive indene and furanone moieties which are attached tothe light-sensitive polymers of this invention can be represented by thefollowing structural formulae:

wherein R is an aromatic group such as a phenyl group, a phenyl groupsubstituted with such substituents as an alkyl group of 1 to 8 carbonatoms (e.g., methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl,etc.), an alkoxy group of 1 to 8 carbon atoms (e.g., methoxy, ethoxy,propoxy, butoxy, amyloxy, hexyloxy, heptyloxy, octyloxy, etc.) analkoxycarbonyl group of 2 to 9 carbon atoms (e.g., methoxycarbonyl,ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, amyloxycarbonyl,hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, etc.), a nitrogroup, a halogen group (e.g., bromo, chloro, iodo), etc.; a naphthylgroup, a naphthyl group substituted with one or more of the above namedsubstituents, a furyl group, a furyl group substituted with one or moreof the above-named substituents or with an indenylidenemethyl group;each R is a hydrogen atom, an alkyl group of 1 to 8 carbon atoms (e.g.,methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, etc.) or analkoxy group of 1 to 8 carbon atoms (e.g., methoxy, ethoxy, propoxy,butoxy, amyloxy, hexyloxy, heptyloxy, octyloxy, etc.); R is a cyanogroup or an alkoxycarbonyl group of 2 to 9 carbon atoms (e.g.,methoxycarbouyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl,amyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbouyl,etc.); R is an aryl group such as phenyl, substituted phenyl, naphthyl,substituted naphthyl, etc.; X is a carbonyloxy linkage, the oxygen atomof which is attached to the polymer backbone, an oxycarbonyl linkage,the carbonyl group of which is attached to the polymer backbone, or anamido linkage; Z is an arylmethylidyne group (e.g., a phenylmethylidynegroup); m is OorlandnisOor 1.

Representative carboxylic acids and alcohols, the derivatives of whichcan be employed to prepare light-sensitive polymers having the abovegroups attached to the polymer backbone include:

l-arylmethylene-3-indenecarboxylic acids such asl-benzylidene-3-indenecarboxylic acid,l-p-nitrobenzylidene-3-indenecarboxylic acid,1-p-chlorobenzylidene-3-indenecarboxylic acid,l-p-methoxybenzylidene-3-indenecarboxylic acid,1-p-ethoxycarbonylbenzylidene-3-indenecarboxylic acid,1-p-(2-ethylhexoxy)benzylidene-B-iudenecarboxylic acid,1-furfurylidene-3-indenecarboxylic acid, I- [5-( 3-methoxycarbonyll-indenylidenemethyl) furfurylidene]-3-indenecarboxylicacid, 4,7-dimethyl-l-p-isopropylbenzylidene-3-indenecarboxylic acid,4,7-diethyl-1-p-methoxybenzylidene-3-indcuecarboxylic acid,5,6-dimethoxy-l-p-(Z-ethylhexoxycarbonyl) benzylidene-3-indenecarboxylicacid; 1-indenylidenemethylaromatic acids, such as3-methoxycarbonyl-l-iudenylidenemethylbenzoic acid,3-(2-ethylhexoxycarbonyl)-l-indenylidenemethylbenzoic acid,3-cyano-1-indenylidenemethylbenzoic acid,3-methoxycarbonyl-l-indenylidenemethylcinnamic acid,3-(2-ethylhexoxycarbonyl)-1-indenylidenemethylcinnamic acid,3-cyano-l-indenylidenemethylcinnamic acid,p-[4,7-dimethyl-3-(2-ethylhexoxycarbonyl)-l-indenylidenemethyl]benzoicacid, p-(4,7-dimethyl-3-methoxycarbonyl-l-indenylidenemethyDcinnamicacid, p- (5 ,6-dimethoxy-3-methoxycarbonyll-indenylidenemethyDbenzoicacid, 1-arylmethylene-3-indenemethanols, such as,1-benzylidene-tat-phenyl-3-indenemethanol,1-p-nitrobenzylidene-a-phenyl-3-indenernethanol,1-p-methoxybenzylidene-a-phenyl-3-indenemethanol, l-p-(Z-ethylhexoxycarb onyl) benzylidene-a-phenyl- 3-indenemethanol,4,7-dimethyl-l-p-isopropylbenzylidene- S-indenecarboxylic acid;S-arylmethylene-Z(5H)-furanone-3-carboxylic acids, such as5-benzylidene-2(5H)-furanone-3-carboxylic acid,5-(p-nitrobenzylidene)-4-phenyl-2(5H)-furanone- 3-carboxylic acid,5-(p-ethoxybenzylidene)-2(5H)-furanone- 3-carboxylic acid,5-[p-(Z-ethylhexoxy)benzylidene]-2(5H)-furanone- 3-carboxylic acid,5-(p-ethoxycarbonylbenzylidene)-2(5H)-furanone- 3-carboxylic acid; and2(5H)-furanone-5-ylidenemethylaromatic acids, such as p- 3-methoxycarbonyl-4-phenyl-2 (5 H) -furanon- S-yIidenemethyl) cinnamic acid,

p- 3-ethoxycarbonyl-4-phenyl-2 5H) -furanon- 5-ylidenemethyl benzoicacid,

p- 3- (Z-ethylhexoxycarbonyl -4-phenyl-2 (5 H)furanon-S-ylidenemethyl]cinnamic acid,

p- 3-cyano-4-phenyl-2 5H) -furanon-5-ylidenemethyl) cinnamic acid,

p- 3-cyano-4-phenyl-2 (5 H) -furanon-5-ylidenemethyl) benzoic acid.

The polymers which form the backbone of the lightsensitive polymers ofthis invention and to which the light-sensitive moieties are appendedinclude natural and synthetic resins such as hydroxyl-containingpolymers, for example, polyvinyl alcohol, polyvinyl alcohol-co-vinylacetate, polyvinyl alcohol-co-vinyl benzoate, polyvinyl alcohol-co-vinylacetate-co-vinyl benzoate, polyethers such as epoxy and phenoxypolymers, e.g., the condensation product of a bisphenol, such asdiphenylolpropane, with epichlorohydrin, naturally occurring materialssuch as cellulose, starch, guar, alginic acid, and their partiallyesterified or etherified derivatives, polyesters of polyhydroxyintermediates such as glycerol and sorbitol which have hydroxyl groupsremaining after incorporation in the polymer chain; polymers containingreactive amino groups, for example, aminostyrene and anthranilic acidpolymers such as polyvinyl anthranilate; polymers containing reactiveanhydride groups such as copolymers of maleic anhydride with ethylene orstyrene.

The light-sensitive polymers of the present invention are prepared byreaction of the hydroxy or amino groups on the polymer backbone with anacid halide of the lightsensitive I arylmethyleneindene or 5arylmethylene- 2(5H)-furanone moiety, or by reaction of the hydroxylderivatives of the l-arylmethyleneindene moiety with a polymercontaining reactive anhydride groups. This reaction is typically carriedout in a tertiary amine solvent such as pyridine, picoline, lutidine,triethylamine, and the like, at room temperature, or at elevatedtemperatures up to about C.

When the hydroxyl-containing polymer employed is a polyvinyl alcohol,light-sensitive polymers which have good solubility and other desirablephysical properties can be prepared by the procedure described incopending Reynolds US. patent application Ser. No. 812,380, entitled AProcess for the Preparation of Soluble Polyvinyl esters, filed Apr. 1,1969 now US. Pat. 3,560,465, patented Feb. 2, 1971. The procedureinvolves swelling the polyvinyl alcohol in a tertiary amine solventfollowed by partial esterification with an aroyl chloride such asbenzoyl chloride. The partially aroylated polyvinyl alcohol is thenesterified with the photo-sensitive acid chloride, after which anyremaining hydroxy] groups optionally can be esterified with aroylchloride.

The light-sensitive l-arylmethylene indene andS-arylmethylene-2(5H)-furanone derivatives which are employed inpreparing light-sensitive polymers of the present invention can beprepared by the reaction of a 3-indenecarboxylic acid or a 3-furanonecarboxylic acid with an aromatic aldehyde. Suitable aromati aldehydesinclude benzaldehyde, benzaldehyde substituted with such groups atnitro, alkyl, alkoxy, alkoxycarbonyl, carboxy, chloro, and the like;p-formylcinnamic acid; naphthaldehyde, naphthaldehyde substituted withthe above substituents; 2- furaldehyde; substituted furaldehydes; andthe like. This reaction is carried out in aromatic hydrocarbon solvents,such as toluene, in the presence of an amine salt, such as piperidineacetate, at elevated temperature in the range of 80 to C. The resultingcarboxylic acid can be converted to the acid halide by treatment with ahalogenating agent such as oxalyl chloride or thionyl chloride. Thehydroxyl derivative of indene can be prepared by c0ndensation of indenewith an aromatic aldehyde in alcoholic potassium hydroxide.

In addition to the light-sensitive group, the polymers of this inventioncan contain non-light-sensitive groups attached to the polymer backbone.Such other groups are often used in modifying the physical properties ofthe polymer, such as solubility, adhesivity, melting point, and thelike. Useful groups include those derived from aliphatic and aromaticcarboxylic acids, such as acetic acid, haloacetic acid, propionic acid,isovaleric acid, succinic acid, glutaric acid, adipic acid, sebacicacid, 2-ethylhexanoic acid, decanoic acid, benzoic acid, halobenzoicacids, nitrobenzoic acids, toluic acids, p-ethylbenzoic acid,p-octylbenzoic acid, p-ethoxybenzoic acid, p-amyloxybenzoic acid,Z-naphthoic acid, and the like. These modifying groups can be attachedto the polymer prior to addition of the light-sensitive group, forexample, when an acetylated polyvinyl alcohol is used as the polymerbackbone, or when the procedure of the Reynolds application, referred toabove, is employed to prepare the light-sensitive polymers of thisinvention. Alternatively, free reactive groups contained on the polymerbackbone after addition of the light-sensitive moiety can be esterifiedwith the acid chloride, or other suitable reactants, of these modifyinggroups. The modifying group can comprise up to 75% of the groupsattached to the polymer backbone. Thus, as few as 25% of the groupspendant from the polymer backbone can be light-sensitive groups of thepresent invention. Preferably, 25 to 85% of the groups attached to thepolymer backbone are light-sensitive groups of this invention.

The polymers of the present invention are useful in a variety ofphotographic applications to prepare photomechanical images such aslithographic printing plates and photoresists.

Coating compositions containing the light-sensitive polymers of thisinvention can be prepared by dispersing or dissolving the polymer in asuitable organic solvent such as dimethylformamide; ketones such as4-methyl-2- pentanone, cyclohexanone, etc.; chlorinated hydrocarbonsolvents such as chloroform, trichloroethylene, dichloroethane,trichloroethane, tetrachloroethane, etc.; mixtures of these solvents,and the like. Coating compositions can include a variety of photographicaddenda utilized for their known purpose, such as agents to modify theflexibility of the coating, agents to modify its surfacecharacteristics, dyes and pigments to impart color to the coating,agents to modify the adhesivity of the coating to the support, and avariety of other addenda known to those skilled in the art.

The coating compositions can be sensitized with such sensitizers aspyrylium and thiapyrylium salts, thiazoles, benzothiazolines,napththothiazolines, quinolizone, Michlers ketone, Michlers thioketone,and the like sensitizers. Because of the wide range of spectral responseand high photographic speed of the light-sensitive polymers of thepresent invention, often it is not necessary, and for some applicationsnot desirable, to incorporate sensitizers in the photosensitive coatingcomposition. If, however, a sensitizer is employed, it can be present inamounts of about 0.005 to 5 percent by weight of the coatingcomposition.

The light-sensitive polymer of this invention can be the sole polymericconstituent of the coating composition or another polymer can beincorporated therein to modify the physical properties of thecomposition and serve as a diluent. For example, phenolic resins, suchas thermoplastic novolac resins, can be incorporated in the compositionto improve the resistance of the polymer composition to etchants when itis used as a photoresist. Similarly, hydrophilic polymers such ascellulose and its derivatives, polyalkylene oxides, polyvinyl alcoholand its derivatives, etc., can be incorporated in the composition toimprove the hydrophilic properties of the coating when it is used in thepreparation of lithographic printing plates. These other polymericmaterials can constitute 6 up to 25% by weight, based on the weight ofthe lightsensitive polymer, of the coating composition.

Photosensitive elements can be prepared by coating the photosensitivecompositions from solvents onto supports in accordance with usualpractices. Suitable support materials include fiber base materials suchas paper, polyethylene-coated paper, polypropylene-coated paper,parchment, cloth, etc.; sheets and foils of such metals as aluminum,copper, magnesium, zinc, etc.; glass and glass coated with such metalsas chromium, chromium alloys, steel, silver, gold, platinum, etc.;synthetic polymeric materials such as polyalkyl methacrylates (e.g.polymethyl methacrylate), polyester film base (e.g., polyethyleneterephthalate), polyvinyl acetals, polyamides (e.g., nylon), celluloseester film base (e.g., cellulose nitrate, cellulose acetate, celluloseacetate propionate, cellulose acetate butyrate), and the like. Theoptimum coating thickness for a particular purpose will depend upon suchfactors as the use to which the coating will be put, the particularlight-sensitive polymer employed, and the nature of other componentswhich may be present in the coating. Typical coating thicknesses can befrom about 0.1 to 10 mils.

Photomechanical images can be prepared with photosensitive elements byimagewise exposing the element to a light source to harden orinsolubilize the polymer in exposed areas. Suitable light sources whichcan be employed in exposing the elements include sources rich in visibleradiation and sources rich in ultraviolet radiation, such as carbon arclamps, mercury vapor lamps, fluorescent lamps, tungsten lamps,photoflood lamps, and the like.

The exposed element can be developed with a solvent for the unexposed,uncrosslinked polymer which is a nonsolvent for the exposed hardenedpolymer. Such solvents can be selected from the solvents listed above assuitable coating solvents, as Well as others.

The following examples further illustrate the practice of the presentinvention.

Example 1.Preparation of 1-benzylidene-3- indenecarboxylic acid Example2.-Preparation of l-p-nitrobenzylidene-3- indenecarboxylic acid1-p-nitrobenzylidene-3-indenecarboxylic acid is made in 57 percent yieldby the above procedure except that pnitrobenzaldehyde is used instead ofbenzaldehyde and the recrystallization solvent is dioxane.

Example 3.-Preparation of l-p-methoxybenzylidene- 3-indene carboxylicacid A solution of 40 g. (0.25 mole) of 3-indenecarboxylic acid and 35g. (0.26 mole) of p-anisaldehyde in 320 ml. of methanol is treated withml. of 30 percent potassium hydroxide in methanol. The mixture isallowed to stand overnight in a cold water bath and then is added to 500ml. of water. Extraction of this mixture with ether, acidification ofthe aqueous phase, collection of the solid, washing with water, anddrying at 60 C. gives 61 g. of product, M.P. 198200 C. Recrystallizationfrom chlorobenzene gives 41 g. (59 percent) of yellow crystals, M.P. 222C.

Example 4.-Preparation of methyll-p-carboxybenzylidene-3-indenecarboxylate A mixture of 10.7 g. (0.0713mole) of p-carboxybenzaldehyde 12.4 g. (0.0713 mole) methyl3-indenecarboxylate, 1 ml. of piperidine, 1 ml. of glacial acetic acid,and 150 ml. of toluene is refluxed for 2 hours with stirring andazeotropic removal of water. The mixture is cooled overnight in therefrigerator and the solid collected, washed with toluene, and dried at60 C. to give 19.0 g. of orange crystals, M.P. 250 C. Recrystallizationfrom 350 ml. of dioxane gives 14.2 g. (65.0 percent), M.P. 274- 276 C.

Analysis.--Calcd. for C H O (percent): C, 74.5; H, 4.57. Found(percent): C, 74.8 H, 4.7.

Example 5.Preparation ofp-[3-methoxycarbonyll-indenylidenemethyl]cinnamic acid p-[3methoxycarbonyl-l-indenylidenemethyl]cinnamic acid, M.P. 251-254 C. ismade in 68.5 percent yield by the procedure of Example 4 except thatp-formylcinnamic acid is used in place of p-formylbenzoic acid.

Analysis.--Calcd. for C H O (percent): C, 75.8; H, 4.82. Found(percent): C, 76.3; H, 5.1.

Example 6.Preparation of Z-ethylhexyl 3- indenecarboxylate A solution of200 g. (1.25 mole) of 3-indenecarboxylic acid, 2 liters of2-ethyl-1-hexanol, and 5 g. of p-toluenesulfonic acid is distilledslowly through a 6-inch column packed with fit-inch glass helices for 5hours, refluxed over night, and then distilled for 4 more hours. Duringthis time the pot temperature rises from 160 to 190 C.; and 26 ml. ofwater is distilled off. The mixture is concentrated at the water pumpand the residue dissolved in 1 liter of petroleum ether (B.P. 35-60 C.)and allowed to stand overnight. The filtered solution is washed with 500ml. of water, 200 ml. of saturated aqueous sodium bicarbonate, and againwith 500 ml. of water. Drying over anhydrous sodium sulfate,concentration at the water pump and fractionation of the residue gives12.2 of forerun, B.P. 128-181 C. (1 mm.), 143 g. of pale yellow oil,B.P. 165-166 C. (1 mm.), 11 1.5195 and 64.5 g. B.P. 165-169 C (1 mm.) rz1.5186. The yield of 207.5 g. is 61.0 percent of the theoreticalquantity.

AnaIysz's.Calcd. for C H O (percent): C, 79.4; H, 8.83. Found (percent):C, 79.4; H, 8.4.

Example 7.Preparation of p-[3-(2-ethylhexoxycarbonyl-l-indenylidenemethyl] cinnamic acid A mixture of 198 g. (0.728 mole) of2-ethylhexyl 3- indenecarboxylate prepared in Example 6, 128 g. (0.728mole) of p-formylcinnamic acid, 1 liter of toluene, 3 ml. of piperidineand 3 ml. of glacial acetic acid is refluxed for 24 hours with stirringand azeotropic removal of water. The hot solution is gravity filteredand the filtrate is cooled overnight in the refrigerator. The solid iscollected, boiled with 3 liters of acetonitrile, chilled overnight, andagain collected and dried to give 171.3 g. (54.8 percent) of orangeproduct, M.P. 147.5150 C.

Analysis.-Calcd. for C H O (percent): C, 78.2; H, 6.98. Found (percent):C, 77.9; H, 6.9.

Example 8.-Preparation of 1-benzylidene-3- indenecarbonyl chloride To amixture of 30.4 g. (0.114 mole) of l-benzylidene- 3-indenecarboxylicacid prepared in Example 1, 200 ml. of benzene, and 1 m1. ofdimethylformamide is added dropwise with stirring 31.8 g. (0.251 mole)of oxalyl chloride. After completion of the addition the mixture isstirred for minutes at room temperature and then for 2 hours on thesteam bath. The solution is cooled to room temperature, filtered from asmall amount of tar, diluted with 200 ml. of ligroine (B.P. 6375 C.),and cooled overnight in the refrigerator. The solid is collected to give22.4 g. of brown-yellow crystals, M.P. 113-121 C. Recrystallization from200 ml. of cyclohexane gives 19.2 g. (6.32 percent) of orange crystals,M.P. 119-122 C- 8 Analysis.Calcd. for C H ClO (percent): C, 76.5; H,4.13; CI, 13.3. Found (percent): C, 76.2; H, 4.4; Cl, 13.5.

Example 9.-Preparation of methyl1-[p-(2-chlorocarbonylvinyl)-benzylidene]-3-indenecarboxylate Methyl1-[p-(2 chlorocarbonylvinyl)benzylidene]-3- indene carboxylate is madeby the procedure of Example 8 fromp-(3-methoxycarbonyl-l-indenylidenemethyl)cinnamic acid prepared inExample 5 and oxalyl chloride (10 percent excess) in 57 percent yield,M.P. 148-15 1 C. after recrystallization from benzene.

Analysis.-Calcd. for C H ClO (percent): C, 71.8; H, 4.29; Cl, 10.1.Found (percent): C, 72.1; H, 4.5; Cl, 10.3.

Example 10.--Preparation of methyll-p-chlorocarbonylbenzylideneindene-3-carboxylate,l-p-methoxybenzylidene-3-indenecarbonyl chloride and1-p-nitrobenzylidene-3-indenecarbonyl chloride Methyl 1 pchlorocarbonylbenzylideneindene-3-carboxylate,l-p-methoxybenzylidene-3-indenecarbonyl chloride, and1-p-nitrobenzylidene-3-indenecarbonyl chloride are made by treatment ofthe appropriate acids from Examples 4, 3 and 2 with 10 percent excess ofoxalyl chloride by the procedure described above except that it is notnecessary to dilute with ligroine in order to get the products tocrystallize.

Example 11.Preparation ofp-[3-(2-ethylhexoxycarbonyl)-1-indenylidenemethyl]cinnamoyl chloride p[3-(2-ethylhexoxycarbonyl)-l-indenylidenemethyl] cinnamoyl chloride ismade from the corresponding acid prepared in Example 7 and oxalylchloride by the above procedure except that after completion of thereaction the solution is concentrated at the water pump. Slurrying theresidue with ligroine (B.P. 63-75 C.) gives a solid which is collectedand recrystallized from the same solvent to give the orange, crystallineproduct, M.P. 5961 C. in 75 percent yield.

Analysls-Calcd. for C H ClO (percent): C, 74.9; H, 6.46; CI, 7.92. Found(percent): C, 74.8; H, 6.2; Cl, 8.2.

Example l2.Preparation of copoly[vinyl acetate-covinylbenzoate-co-vinyll-benzylidene 3 indenecarboxylate] A mixture of 5.0 g. (0.10 mole) of amedium molecular weight, 12 percent acetylated poly(vinyl alcohol)(Elvanol 52-22 sold by Du Font) and 200 ml. of pyridine (dried overLinde molecular sieve, 3A powder) is stirred overnight on the steambath, cooled to room temperature and treated with 16.5 g. (0.0618 mole)of 1-benzylidene-3- indenecarbonyl chloride prepared in Example 8. Themixture is stirred for 15 minutes without heating and then for 2 hoursat 50 C. It is then cooled to 25 C., treated with 7 g. (0.05 mole) ofbenzoyl chloride and heated 1 hour at 50 C. Cooling to room temperature,precipitation in water, leaching overnight in fresh water, collection ofthe solid and drying to constant weight in a vacuum desiccator overanhydrous calcium chloride gives 21.8 g. of pale yellow product(hereafter identified as Polymer 1). Similarly, copoly(vinylacetate-co-vinyl benzoate-co-vinyl-l-p-methoxybenzylidene 3indenecarboxylate) (Polymer 2) and copoly(vinyl acetate-covinylbenzoate-co-vinyl 1-p-nitrobenzylidene-3-indenecarboxylate) (Polymer 3)are made by esterification of Elvanol 5222 with appropriate acidchlorides of Example 10 by this procedure.

Example l3.-Sensitometric data Solutions containing 2 percent of thepolymers of Example 12 in dichloroethane are coated and evaluated togive the sensitometric data in Tables 1 and 2. The photographic speedand spectral response of the polymers is determined by the procedure ofL. M. Minsk et al. Photosensitive Polymers, I and II Journal of AppliedPolymer Science; vol. II, No. 6, pp. 302-311 (1959). The sensitivityvalue is a measure of the relative speed of the TABLE 3 Polymers of thetype polymer, when exposed to ultraviolet or visible light, j comparedwith the speed of unsensitized polyvinyl cin- -0 0 eHs namate as astandard. The coating and developing solvents used in this andsubsequent examples are identified as f follows: Tom- E 7.DCE1,2-dichloroethane Q T CE-trichl0r0ethane O=('](CH=CH)|1 CH TCEtetrachloroethane =1 MEK-methyl ethyl ketone 000RDMFN,N-d1methylformam1de 1 t I CHXcyclohexanone Mo e The sensitizersemployed in this and subsequent examples sen s fii eare present inconcentrations of 0.2 percent by weight, Polymer R Acetate Bmwate esterand are identified as follows: 4 OH 0 12 00 2s 5 CH; 1 12 01 27 (A)2,6-b1s(p-ethoxyphenyl) 4 (p-n-amyloxyphenyl) 0 thiapyrylium perchlorate6 1 12 63 B) Zhenzoylmethylene-l-methyl 18 naphthothiazon-GdIr lme 7Ssmeasabove 1 12 38 5 (C) 4-H-qu1nol1z1ne-4-th1one 8 .-do 1 12 13 7% (D)methyl 3-rnethyl-2-benzothiazolidinedithioacetate 2 9 1 12 8 TABLE 4Sensitivity value of the polymers described in Table 3 Coating andSensitivity value using sensltizer developing Polymer solvent None 1 A BC D E F (E) fi-dimethylaminoi-methylcoumarin (F) erythrosin (G)1,2-benzanthraquinone {OKs-C -{CHr-CH9- -{CHr-CH3- 1 1 Q --C CH; -EC1H:i

TABLE 1.-SENSIT1VITY VALUE FOR POLYMERS OF THE TYPE Mole per- Coatingcentlightand Sensitivity value using sensitizer: 1

sensitive developing R ester solvent None 1 A B C D E Polymer:

1 H 62 DCE 1,600 2,200 740 1,600 2 CHgO 44 DCE 250 170 170 170 250 3 N0T4010 500 760 350 1,100 1,100 120 1 Control.

8 T TABLE a pee r response Spectral response in my Polymer Polymersensitize 1 2 3 Sensitizer 4 a e 7 s 9 (None) Control 260-520 240490275-5625 A 260-590 50-490 270- Control" 35M .11---- 300-575 B 0--270-530 05 g Example 14 F::::::::::::::::::::

Example 15.--Preparation of copoly[2-(l-benzylidene-3-indene-carbonyloxy)trimethylene 2,2-bis(4-oxyphenyl)propane;2(benzoyloxy)trimethylene-2,2-bis(4-oxyphenyl) propane] A solution of17.0 g. (0.0599 mole) of Phenoxy Resin (Union Carbide PRDA 8030) in ml.of dry pyridine is treated with 8.0 g. (0.030 mole) of 1-benzy1idene-3-indenecarbonyl chloride prepared in Example 8, stirred for /2 hourwithout heating and then for 1 hour at 50-60 C. After being cooled toroom temperature the solution is treated with 4.6 g. (0.033 mole) ofbenzoyl chloride, stirred for 15 minutes without heating, then for 1hour at 50-60" C., and then cooled to room temperature. The product isisolated by precipitation in water and dried to constant weight in avacuum desiccator over anhydrous calcium sulfate. The yield is 22.1 g.of pale yellow powder (Polymer Treatment of the Phenoxy Resin with anequimolar quantity of 1-benzylidene-3-indenecarbonyl chloride preparedin Example 8 by this procedure (except that the benzoyl chloride isomitted) gives poly[2-(1-benzylidene-3-indenecarbonyloxy)trimethylene2,2-bis (4-oxyphenyl)propane], (Polymer 11). Similar treatment withp-[3-(2-ethylhexoxycarbonyl) 1 indenylidenemethyl] cinnamoyl chlorideprepared in Example 11 gives poly {{2-{p-[3 (2ethylhexoxycarbonyl)indenylidenemethyl]cinnamoyloxy}trimethylene 2,2bis(4 oxyphenyl) propane}}, Polymer 12. Sensitometric data for thesepolymers are given in Table 6.

TABLE 6 brown solution is added slowly with manual stirring to 2 litersof water. The mixture is filtered. Acidification of the milky filtratewith concentrated hydrochloric acid gives a pale yellow solid which iscollected and vacuum dried to give 17.0 g. of yellow product,

A33 286, 345 nm.

Example l7.1-furfurylidene-3-indenecarboxylic acid A mixture of 32.0 g.(0.200 mole) of 3-indenecarboxylic acid, 19.2 g. (0.200 mole) of2-furaldehyde, 200 ml. of toluene, 1 ml. of glacial acetic acid, and 1ml. of piperidine is refluxed for 3 hours with stirring and azeotropicSensitivity values for polymers or the type CH: 1 OH I $CC:H5 (EH:(5-0-3 CE:

I ll

Coating Sensitivity value and de- Mole Percent with sensitizer valopingPolymer R solvent R Benzoate None 1 A B C 10 j DCE 50 11 45 14 63 I CH-CH;

11 DCE 100 0 45 89 45 63 CH-CsHu 12 n-CtHe DCE 100 0 13 45 23 130 C 0 OCHzilHCHzCH:

I 11-- JH=oH- 1 Control Example16.-Copoly[ethylene-u-(l-benzylidene-B-indenyl) benzyl hydrogen maleate](oooH on -ant -CHOH- removal of 3.0 ml. of water. The solid whichseparates upon cooling to room temperature is recrystallized from 250ml. of dioxane to give 23.7 g. (49.8 percent) of orange crystals, M.P.246-254 C.

Analysis.-Calcd. for C H O (percent): C, 75.6; H, 4.20. Found (percent):C, 75.3; H, 4.4. Similar treatment of 29.2 g. (0.304 mole) of2-furaldehyde with 52.8 g. (0.304 mole) of methyl 3-indenecarboxylategives after 3 recrystallizations from methanol 50.4 g. (65.8 percent) oforange crystalline methyl 1- furfurylidene-3-indenecarboxy1ate, M.P.98.5- C.

Analysis.-Calcd. for C H O (percent): C, 76.2; H, 4.76. Found (percent):C, 75.9; H, 5.0.

Example l8.Methyl 1-( 5-formylfurfurylidene)-3- indenecarboxylate To 100ml. of dimethylformamide is added, with stirring and cooling to keep thetemperature below 30 C., 7.7 g. (0.050 mole) of phosphoryl chloridefollowed by 12.6 g. (0.0500 mole) of methyll-furfurylidene-3-indenecarboxylate. The mixture is stirred for 1 hourwithout heating and then for 1 hour at 70 C., chilled in ice, and

13 made basic by slow addition of 2 N potassium hydroxide. The solid iscollected, washed with water, and recrystallized 4 times fromacetom'trile to give 4.6 g. (33 percent) of orange crystals, M.P. 157-158.5 C.

Analysis.-'Calcd. for C H O' (percent): C, 72.7; H, 4.28. Found(percent) C, 72.9; H, 4.2.

When the reaction is run as described above with twice the amount ofmaterial, and the potassium hydroxide treatment is omitted, a red-browncrystalline solid separates after stirring overnight at roomtemperature. 'It is collected, washed with ether, and air dried to give25.4 g. which liquefies at 100 C., resolidifies, and melts at 1-51-155C. This Vilsmeier product gives methyl 1-(5-formylfurfurylidene) 3indenecarboxylate when treated with alcohols and condenses with activemethylene compounds to give products identical with those from1-(5-formylfururylidene)-3-indenecarboxylate.

Example 19.-Methyl 1-[5-(3-carboxy-l-indenylidenemethyl)furfurylidene]-3-indenecarboxylate A mixture of 25.0 g. of the Vilsmeir product fromthe preceding example, 11.6 g. (0.0728 mole) of 3-indenecarboxylic acid,and 200 ml. of methanol is warmed until solution results, treated with 1ml. of piperidine, and allowed to stand for 72 hours. The solid iscollected, washed with methanol, and recrystallized twice from dioxaneto give 11.9 g. (39.8 percent) of brown crystals, M.P. 272.5-273.5 C.

Analysis.Calcd. for C H O (percent): C, 76.8; H, 4.38. Found (percent):C, 76.8; H, 4.6.

Example20.1-[5-(3-methoxycarbonyl-l-indenylidenemethyl)furfurylidene]-3-indenecarbonylchloride To a mixture of 8.6 g. (0.0200 mole) of methyl 1-[5- (3 carboxyl-indenylidenemethyl)furfurylidene1-3-indeneocarboxylate, 1 m1. of DMF,and 100 ml. of benzene is added dropwise with stirring 2.8 g. (0.022mole) of oxalyl chloride. The mixture is stirred for 1 hour withoutheating and then for 1 hour on a steam bath. After cooling to roomtemperature the solid is collected, washed with benzene, andrecrystallized from diox-ane to give 5.2 g. (60 percent) of shinyred-brown crystals, M.P. 218- 220 C.

Analysis.Calcd. for C I-I ClO (percent): C, 72.8; H, 3.96; CI, 8.34.Found (percent): C, 72.6; H, 4.3; CI, 8.1.

Similar treatment of 15.3 g. (0.0643 mole) of 1furfurylidene-3-indenecarboxylic acid in 200 ml. of benzene containing 1ml. of DMF with 9.0 g. (0.071 mole) of oxalyl chloride, dilution of thereaction mixture with 800 ml. of ligroine (B.P. 66-75 C.), collection ofthe solid which separates upon standing overnight, and recrystallizationfrom 600 ml. of cyclohexane gives 7.3 g. (44.2 percent) of1-furfurylidene-3-indenecarbonyl chloride as orange threads, M.P.Ill-116 C.

Analysis.Calcd. for C H Cl0 (percent): C, 70.0; H, 3.50; Cl, 13.8. Found(percent): C, 70.2; H, 3.8; CI, 13.9.

Examp1e 21.Copoly(vinyl acetate-vinyl Z-ethylhexanoate-vinyl1-furfurylidene-3-indenecarboxylate nCdh-CH i To a mixture of 2.8 g.(0.057 mole) of Elvanol 52-22 in 100 ml. of pyridine which has beenstirred overnight on a steam bath and then cooled to room temperature isadded 2.3 g. (0.014 mole) of 2-ethylhexanoyl chloride. The mixture isstirred for 2 hours, treated with a slurry K 309, 324, 338, 402 nm.

Coating and developing solvent Sensitizer Example 22Copoly{vinylacetate-vinyl 2-et-hylhexanoate-vinyl 1-[5-(3-methoxycarbonyl-l-indenylidenemethyDfurfurylidenel-S indenecarboxylate} ---0 HUGE 0The procedure of Example 21 is followed using 1.2 g. (0.024 mole) ofElvanol 52-22 in 60 ml. of pyridine with successive additions of 1.0 g.(0.0060 mole) of 2-ethylhexanoyl chloride, a slurry of 5.2 g. (0.012mole) of 1 [5 (3 methoxycarbonyl 1 indenylidenemethyl) furfurylidene] 3indenecarbonyl chloride in 50 ml. of 1,2 dichloroethane, and then 1.5 g.(0.0092 mole) of 2-ethylhexanoyl chloride. The polymer is precipitatedfrom the filtered reaction solution by slow addition to 200 ml. portionsof methanol in a blender to give 5.4 g. of red-brown solid,

Mm. ClCHgCl 371, 503 nm.

Coating and developing solvent Sensitizer Example23.--4,7-dimethyl-3-indenecarboxylic acid To a solution of 144 g. (1.00mole) of 4,7-dimethylindene in 500 ml. of ether is added dropwise withstirring at -30 C. under nitrogen a solution of n-butyllithium from 21.5g. of lithium and 171 g. of l-bromobutane (made by the proceduredescribed in Gilman, Organic Reactions, vol. VI, page 352). The mixtureis stirred for 10 minutes after completion of the addition and thenpoured onto 1500 g. of crushed Dry Ice under 500 ml. of ether. Themixture is warmed to 5 C. on a steam bath and extracted 4 times with atotal of 2 liters of water. Acidification of the combined aqueousportions, collection of the solid, and recrystallization from 4 litersof benzene gives 104 g. (55.4 percent) of colorless crystals, M.P.182-183.5 C.

Analysis.-Calcd. for C H O (percent): C, 76.6; H, 6.38. Found (percent):C, 76.0; H, 6.6.

Example 24.Methy1 4,7-dimethyl-3-indenecarboxylate A solution of 100 g.(0.532 mole) of 4,7-dimethyl-3- indenecarboxylic acid, 2 liters ofmethanol and 4 g. of p-toluenesulfonic acid is refluxed overnight,concentrated at the water pump, and then diluted with 500 ml. ofligroine (B.P. 35-60 C.) and chilled. After filtration from a trace ofsolid the solution is washed with 100 ml. of water, 100 ml. of 9 percentaqueous sodium bicarbonate, and then 100 ml. of water, dried withanhydrous sodium sulfate, and concentrated on a steam bath. Distillationof the residue gives 65.3 g. (60.8 percent of yellow oil, B.P. 165-174C.) (10 mm.), 21 1.5506.

Analysis.Calcd. for C H O (percent): C, 77.2; H, 6.9. Found (percent):C, 76.9; H, 6.9.

Example 25.-4,7-dimethyl-1-p-isopropylbenzylidene-3- indenecarboxylicacid The procedure of Example 1 is followed using 29.0 g. (0.154 mole)of 4,7-dimethyl-3-indenecarboxylic acid, 22.8 g. (0.154 mole) ofp-isopropylbenzaldehyde, 200 ml. of toluene, 1 ml. of piperidine, and 1ml. of glacial acetic acid. Concentration at the water pump andrecrystallization of the residue from benzene gives 11.7 g. (23.9percent) of orange crystals, M.P. 185-187 C.

Analysis.Calcd. for C H O (percent): C, 82.9; H,

6.9. Found (percent): C, 82.8; H, 6.6. Similar treatment of 45.8 g.(0.227 mole) of methyl 4,7-dimethyl-3-indenecarboxylate in 500 ml. oftoluene with 40.0 g. (0.227 mole) of p-formylcinnamic acid, collectionof the solid which separates upon cooling, and recrystallization from400 ml. of glacial acetic acid gives 37.7 g. (46.2 percent) of yellowp-(4,7-dimethyl-3-methoxycarbonyl-l-indenylidenemethyl)cinnamic acid,M.P. 185l88 C.

Example 26.4,7-dimethyl-1-p-isopropylbenzylidene-3- indenecarbonylchloride To a solution of 12.0 g. (0.0377 mole) of 4,7-dimethyl-1-p-isopropylbenzylidene-3-indenecarboxylic acid, 2 ml. of DMF, and 100ml. of benzene is added dropwise with stirring 4.75 g. (0.0377 mole) ofoxalyl chloride. After completion of the addition the solution isstirred for 1 hour at room temperature and then for 1 hour on a steambath and then concentrated at the water pump. The yellow solid residueweighed 10.3 g. (81.2 percent). Similar treatment of 20.0 g. (0.0550mole) of p-(4,7-dimethyl-3-methoxycarbonyl-l-indenylidenemethyl)cinnamicacid in 250 ml. of toluene with 7.62 g. (0.0600 mole) of oxalyl chloridegives upon cooling to room temperature, dilution with 200 ml. ofligroine (B.P. 66-75 C.), and collection of the separated solid, 13.2 g.(63.4 percent) of yellow crystallinep-(4,7-dimethyl-3-methoxycarbonyl-l-indenyhdenemethyl)cinnamoylchloride, M.P. 225240 C.

CH3 HCrHr-C H O r N t...

To a mixture of 3.07 g. (0.0614 mole) of Elvanol 52- 22 in 150 ml. ofpyridine which has been stirred overnight on a steam bath and cooled toroom temperature is added 10.3 g. (0.0307 mole) of4,7-dimethyl-l-p-isopropylbenzylidene-3-indenecarbonyl chloride. Themixture is stirred for /2 hour at room temperature and then 3 hours at45- 55 C. It is cooled to room temperature, treated with 5.3 g. (0.033mole) of 2-ethylhexanoyl chloride, stirred for /2 hour at roomtemperature, and then for 2 hours at 45- 55 C. The mixture is cooled toroom temperature and added slowly to 200 ml. portions of methanol in ablender. The precipitated polymer is collected, washed with methanol,and vacuum dried to give 9.5 g. of yellow powder,

ClCHICHZO1311, 378 nm.

max.

Example 28.-Copoly[ vinyl acetate-vinyl p-(4,7-dimethyl-3-methoxycarbonyl 1 indenylidenemethyl)cinnamatevinyl 2-ethylhexanoate]To a mixture of 5.0 g. (0.10 mole) of Elvanol 52-22 and 300 ml. ofpyridine which has been stirred overnight on a steam bath and thencooled to room temperature is added 5.0 g. (0.031 mole) of2-ethylhexanoyl chloride. The mixture is stirred for 1 hour, treatedwith a solution of 17.2 g. (0.0455 mole) ofp-(4,7-dimethyl-3-methoxycarbonyl-l-indenylidenemethyl)cinnamoylchloride in 150 ml. of 1,2-dichloroethane, stirred for 1 hour, treatedwith 4.0 g. (0.025 mole) of Z-ethylhexanoyl chloride, and stirredovernight. The polymer is isolated from the filtered reaction mixture byprecipitation in methanol using a blender, collection, and vacuum dryingto give 20.2 g. of orange solid olomomol 318, 388 nm.

mat.

an Sensldeveltivity oping Sensitizer value solvent Control 89 DCE 250 DCE D CE 110 DCE A solution of 30 g. (0.138 mole) of3-methoxycarbonyl-4-phenyl-2(5I-I)-furanone, 24.2 g. (0.138 mole) ofp-formylcinnarnie acid, 0.5 ml. acetic acid, and 1.5 ml. piperidine in250 ml. of toluene is refluxed with stirring in a flask attached to aDean Stark trap for 1.5 hours during which time 2.3 ml. of water iscollected. The mixture is cooled, the solid collected by filtration andrecrystallized twice from 300 ml. portions of dioxane to yield 32.4 g.of 5[p-(Z-carboxyvinyl)benzylidene]-3-methoxycarbonyl-4-phenyl-2(5H)-furanonemelting at 252-4 C.

Analysis.Calcd. for C H O (percent): C, 70.3; H, 4.3. Found (percent):C, 69.8; H, 4.8.

Example 30.Preparation of 5- [p-(2-chlorocarbonyl) benzylidene] 3methoxycarbonyl-4-phenyl-2(5H)- furanone To a suspension of 27.8 g.(0.074 mole) of 5-[p-(2- carboxyvinyl)benzylidene]-3-methoxycarbonyl 4phenyl-2(5H)-furanone, prepared as described in Example 29, in 150 ml.of benzene and 1 ml. of dimethylformamide is added dropwise withstirring 10.4 g. (0.0814 mole) of oxalyl chloride. The mixture isstirred for one hour at room temperature and then heated at reflux forone hour, during which time a solution results. The solution is dilutedwith an equal volume of ligroine and cooled to 10 C. The solid isseparated by filtration, and recrystallized from 125 m1. of acetonitrileto yield 10.1 g. melting at 247-254 C.

Analysis.--Calcd. for C H ClO (percent): C, 67.0; H, 3.84; Cl, 9.0.Found (percent): C, 67.4; H, 4.3; CI, 8.6.

Example 3l.-Preparation of 5-(p-chlorocarbonylbenzylidene)-3-cyano-4-phenyl-2 (5 H) -furanone To a suspension of 20.8 g. (0.0656mole) of S-(p-carboxybenzylidene)-3-cyano-4-phenyl-2(5H) furanone in 150ml. of benzene and 1 ml. of dimethylformamide is added dropwise withstirring, at room temperature, 9.2 g. (0.072 mole) of oxalyl chloride.The mixture is stirred for 1 hour at room temperature and then for 1hour at reflux at which time a solution resulted. The solution isfiltered and cooled, and then the solid separated by filtration to yield13.1 g. melting at 183-186 C.

Analysis.Calcd. for C H C1NO (percent): C, 68.1; H, 3.0; Cl, 10.6; N,4.1. Found (percent): C, 67.8; H, 3.0; Cl, 10.5; N, 4.1.

Example 32.-Preparation ofS-[p-(Z-chlorocarbonylvinyl)benzylidene]-3-cyano-4-phenyl-2(5H)-furanoneTo a suspension of 25.3 g. (0.0738 mole) of 5-[p-(2-carboxyvinyl)benzylidene]-3-cyano 4 phenyl-2(5H)- furanone in 250 ml. ofo-dichlorobenzene and 2 ml. of dimethylformamide is added dropwise withstirring at room temperature 10.3 g. (0.0812 mole) of oxalyl chloride.The mixture is stirred for 1 hour at room temperature and then is heatedon a steam bath for 1 hour. The mixture is filtered hot and the filtratecooled to room temperature. The solid is collected by filtration. Yield9.8 g., M.P. 229-232" C.

Analysis.-Calcd. for C H ClNo (percent): C, 69.8; H, 3.4; N, 3.9; C1,9.8. Found (percent): C, 68.2; H, 3.6; N, 4.4; Cl, 10.3.

Example 33.-Preparation of copoly[vinyl acetate-vinyl benzoate-vinylp-(3-methoxycarbonyl-4-pheny1-2(5H)- furanone-S-ylidenemethyl)cinnamate]b-oH=oH- CH 0 g G Ll Poly(vinyl alcohol) 2 g. (0.04 mole) [Elvanol52-22, a 12 percent acetylated, medium viscosity poly(vinyl alcohol),sold by Du Pont] is soaked in 80 ml. of dry pyridine on a steam bath forabout 16 hours. The suspension is cooled to room temperature, and 1.4 g.(0.01 mole) of benzoyl chloride is added. The mixture is heated for 1hour at 50 C., cooled to room temperature, and to it is added 7.9 g.(0.02 mole) of 5-[p-(2-chlorocarbonylviny1)benzylidene]-3-methoxycarbonyl 4 phenyl 2 (5H)- 5 furanone prepared asdescribed in Example 30. A slightly exothermic reaction results. Themixture is stirred for minutes, heated at 50 C. for 1 hour, and cooledto 35 C. An additional 1.7 g. (0.012 mole) of benzoyl chloride is added,and the mixture again heated for one hour at 10 50 C., then allowed tostand without heating for about 16 hours. The mixture is poured into 800ml. of water with vigorous stirring to precipitate the polymer. Thesolid is collected by filtration, washed twice with gentle stirring in 1liter portions of water and dried for 48 hours in a 5 vacuum desiccatorto yield 10.7 g. of yellow powder.

A c t DaydlV y m 08 1 0 20 Sensltizer value (1115:.) solven is st v r it5,600 382 CHX MEK 4, 000 500 CHX MEK 5,000 520 CHX MEK 7,900 540 CHX MEK2, 500 520 CHX MEK yl-S-furylidenemethyl)benzoate] powder.

DMF DMF Poly(vinyl alcohol) (Elvanol 52-22) (3.8 g.,. 0.076 mole) issoaked for about 16 hours in ml. of dry pyridine on a steam bath. Aftercooling to 20 C., 2.3 g. (0.019 mole) of isovaleryl chloride is addedand the suspension heated for 1 hour at 50 C. and again cooled to roomtemperature. After cooling, 12.7 g. (0.038 mole) of5-(p-chlorocarbonylbenzylidene) 3 cyano-4-phenyl- 2(5H)-furanone isadded, the mixture stirred for 15 minutes, heated for 1 hour at 50 C.and again cooled to room temperature. After cooling, 2.4 g. (0.020 mole)of isovaleroyl chloride is added, the mixture again heated for 1 hour at50 C.,. and then poured into 800 ml. of vigorously stirred water. Thefinely divided polymer is collected by filtration, washed 4 times with200 ml. portions of water, air dried for 48 hours and then dried in avacuum desiccator for 24 hours to yield 18 g. of yellow To 150 ml. ofdry pyridine is added with stirring at room temperature 7.7 g. (0.0271mole) of Phenoxy Resin PRDA 8030 (Union Carbide Co.). The mixture isstirred until a solution results (3 hours). To the solution is addedwith stirring at room temperature 9.8 g. (0.027 mole) of5-[p-(2-chlorocarbonylvinyl)benzylidene] 3 cyano-4-phenyl-2(5H)-furanone in small portions over a -minute period. Themixture is stirred 10 minutes more, then heated at 50 C. for 1 hour. Asolution results. The dope is cooled to room temperature and poured into800 ml. of vigorously stirred water. The finely divided polymer iscollected by filtration, washed 3 times with 200 ml. portions of water,air dried for 5 hours, then dried in a vacuum desiccator over anhydrouscalcium chloride for 48 hours to yield 12.5 g. of yellow powder.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be elfected within the spirit and scope of theinvention.

What is claimed is:

1. A light-sensitive, linear, film-forming polymer having attached to apolymer backbone, which is the residue of a polymer selected from thegroups consisting of hydroxyl-containing polymers, reactiveamino-containing polymer and reactive anhydride-containing polymers, alight-sensitive moiety selected from the group consisting of 1arylmethyleneindene groups and 5 arylmethylene- 2(5H)-furanone groups,the light-sensitive moiety being attached to the backbone through acarbonyloxy group when the backbone is the residue of ahydroxyl-containing polymer, through an amido group when the backbone isthe residue of a reactive amino-containing polymer and through anoxycarbonyl group when the backbone is the residue of a reactiveanhydride-containing polymer.

2. A light-sensitive polymer as defined in claim 1 wherein thelight-sensitive moiety is the residue of a carboxylic acid selected fromthe group consisting of l-arylmethylene-3-indenecarboxylic acids,1-indenylidenemethylaro matic acids,5-arylmethylene-2(5H)-furanone-3-carboxylic acids and2(5H)-furanon-5-ylidenemethylaromatic acids.

3. A light-sensitive, linear, film-forming polymer comprising a polymerbackbone which is the residue of a hydroxyl-containing polymer, at least25 percent of the hydroxyl units on the polymer backbone beingsubstituted by light-sensitive units derived from a carboxylic acidselected from the group consisting of 1-arylmethy1ene-3-indenecarboxylic acids, 1 indenylidenemethylaromatic acids, 5arylmethylene 2(5H) furanone-B-carboxylic acids and2(5H)-furanon-5-ylidenemethylaromatic acids, the light-sensitive unitsbeing attached to the polymer backbone through carbonyloxy groups.

4. A light-sensitive polymer as defined in claim 3 wherein up to 75percent of the hydroxyl units on the polymer backbone are substituted bynon-light-sensitive units which are the residue of a difi erentcarboxylic acid.

5. A light-sensitive polymer as defined in claim 3 wherein thehydroxyl-containing polymer is the condensation product of a bisphenolwith epichlorohydrin.

6. A light-sensitive polymer as defined in claim 5 wherein thelight-sensitive units are derived from a carboxylic acid selected fromthe group consisting of 1-benzylidene-3-indenecarboxylic acid,l-furfurylidene-3-indenecarboxylic acid,3-(2-ethylhexoxycarbonyl)-l-indenylidenemethylbenzoic acid,3-(2-ethylhexoxycarbonyl)-l-indenylidenemethylcinnamic acid, andp-(4,7-dimethyl-3-methoxycarbonyl-l-indenylidenemethyl)cinnamic acid.

7. A light-sensitive, linear, film-forming polymer comprising a polymerbackbone which is the residue of polyvinyl alcohol, and having at least25 percent of the hydroxyl groups on the polymer backbone substituted bylight-sensitive units which are the residue of a carboxylic acidselected from the group consisting of l-arylmethylene-3-indenecarboxylic acids, l-indenylindene-methylaromatic acids,5-arylmethylene-2(5H)-furanone-3-carboxylic acids and2-(5H)-furanon-5-ylidenemethylaromatic acids, the light-sensitive unitsbeing attached to the polymer backbone through carbonyloxy groups.

8. A light-sensitive polymer as defined in claim 7 wherein thelight-sensitive units are the residue of a carboxylic acid selected fromthe group consisting of 1-benzylidene-3-indenecarboxylic acid,1-furfurylidene-S-indenecarboxylic acid,3-(2-ethylhexoxycarbonyl)-1-indenylidenemethylbenzoic acid,3-(2-ethylhexoxycarbonyl)-1-indenylidenemethylcinnamic acid, andp-(4,7-dimethyl-3-methoxycarbonyl-l-indenylidenemethyl)cinnamic acid.

9. A light-sensitive, linear, film-forming polymer having attached to apolymer backbone which is the residue of a polymer selected from thegroup consisting of hydroxyl-containing polymers, reactiveamino-containing polymers and reactive anhydride-containing polymers, alight-sensitive moiety selected from the group having the followingformulae:

and

groups, and alkoxy groups; R is selected from the group consisting ofalkoxycarbonyl groups and cyano groups; R is an aryl group; X is acarbonyloxy group when the backbone is the residue of ahydroxyl-containing polymer, an amido group when the backbone is theresidue of a reactive amino-containing polymer and an oxycarbonyl groupwhen the backbone is the residue of a reactive anhydride-containingpolymer; Z is an arylmethylidyne group and m and n are each 0 or 1.

10. A light-sensitive polymer as defined in claim 9 wherein the polymerbackbone is the residue of a hydroxyl-containing polymer and X is acarbonyloxy group.

22 References Cited UNITED STATES PATENTS 2,725,372 11/1955 Minsk26091.3

JAMES A. SEIDLECK, Primary Examiner S. M. LEVIN, Assistant Examiner US.Cl. X.R.

10 26032.6 R, 33.8 'EP, 33.8 UA, 75 T, 7-8.5 R, 85.7,

89.7 S, 91.3 VA, 209.6 212, 214, 232, 233.3 R, 233.5, 234-; 9635.1;117-34

